JP3215069B2 - Dry finish for automatic dishwashers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a dry finish for automatic dishwashers.

[0002]

[Prior art]

[0003] In kitchens handling a large amount of dishes, such as hotels, restaurants, schools, hospitals, and employee cafeterias, many automatic dishwashers for automatically washing and drying dishes are installed for rationalization. In the automatic dishwasher, rinsing with water containing a dry finish is usually performed following washing with a detergent. When rinsing is repeated a plurality of times, rinsing with water containing a dry finish is performed at the time of final rinsing.

[0004] The above-mentioned dry finish is used to promote the drying of tableware after rinsing and to obtain a good finish without formation of water droplets (spots) on the tableware. Sucrose fatty acid esters, sorbitan fatty acid esters, and the like, which are excellent in emulsifying power, dispersing power, etc., and which remain in tableware and are safe even in the mouth, are used as main components thereof.

Recently, the use of polyglycerin fatty acid esters has been proposed and attracted attention. For example, "rinsing aid containing polyglycerol fatty acid ester of HLB 3 to 13 as an essential component" (Japanese Patent Application Laid-Open No. 60-53599), or "having a fatty acid having 6 to 18 carbon atoms as a fatty acid residue as an essential component" Rinse Aid Containing Polyglycerin Fatty Acid Ester "(JP-A-59-18709)
No. 6) is known.

[0006]

However, the degree of polymerization of polyglycerol constituting the polyglycerol fatty acid ester, which has been widely used in the past, is named by the average degree of polymerization calculated from the hydroxyl value, and is actually wide. It has a degree of polymerization distribution. For example, although they are distinguished from tetraglycerin, hexaglycerin, and decaglycerin, the degree of polymerization is an average degree of polymerization calculated from the hydroxyl value, and is a mixture of glycerin polymers having a degree of polymerization of 1 to 10 or more. . For this reason, it is inevitable to use a mixture of various polyglycerin fatty acid esters having different surface active properties, and it is not possible to select the most suitable polyglycerin fatty acid ester to be used as a dry finish, and its effect is currently not available. One was not enough.

On the other hand, recently, polyglycerol fatty acid esters have been improved in purity in order to improve the performance (JP-A-63-23837, JP-A-3-8125).
No. 2) and those having a narrow distribution of polymerization degree (Japanese Patent Application Laid-Open No.
JP-A-308560, JP-A-7-100355) have been obtained, and a certain result has been obtained in the improvement of surface active properties such as foaming property, dispersibility, emulsifying property and solubilizing property.

However, in the case of the above-mentioned dry finish, if the foaming property is high, it may cause spots on the contrary, or the water pressure of the water supply pipe in the automatic dishwasher may be reduced. Since the range of hydrophilicity is also limited, the fact that the above-mentioned surface active properties are excellent does not necessarily lead to an excellent dry finishing effect. Therefore, what kind of polyglycerin fatty acid ester is selected to exhibit excellent characteristics for use as a dry finish has not yet been sufficiently studied.

The present invention has been made in view of the above-mentioned circumstances, and a drying finish for an automatic dishwashing machine having an excellent drying finishing effect by using a specific one of various polyglycerin fatty acid esters. The purpose is to provide.

[0010]

In order to achieve the above-mentioned object, the invention according to claim 1 of the present invention provides a method for producing a polymer having a specific polymerization degree n.
Polyglycerin fatty acid obtained by esterifying a polyglycerin containing 50% by weight or more of a single polyglycerin (n = 3, 4, 5) and a fatty acid having (2n) to (2n + 4) carbon atoms It is a dry finish for automatic dishwashers containing esters.

The invention according to claim 2 of the present invention provides:
The polyglycerin fatty acid ester has a carbon number (2n +
It is a dry finish for automatic dishwashing machines using the fatty acid of 2).

That is, the present invention uses a special polyglycerin fatty acid ester containing a single polyglycerin in a high ratio to achieve an excellent balance between low foaming property and hydrophilic property, wettability, dispersibility, solubilization, etc. In addition, an excellent dry finish is obtained. Among the special polyglycerin fatty acid esters, those using a fatty acid having (2n + 2) carbon atoms with respect to the polymerization degree n of single polyglycerin exhibit particularly excellent effects.

[0013]

Next, an embodiment of the present invention will be described.

The polyglycerol fatty acid ester used in the present invention has a specific polymerization degree n (n = any of 3, 4, and 5).
50% by weight (hereinafter referred to as "%")
Abbreviated as above) must be esterified polyglycerols. Of course, the entire polyglycerin may be composed of the single polyglycerin. That is, polyglycerols derived from a plurality of types of polyglycerols having different degrees of polymerization, and polyglycerol fatty acid esters having a wide degree of polymerization distribution are mixed together, which is required for a dry finish, low foaming property and appropriate hydrophilicity. This is because they do not have the same purpose.

The single polyglycerin is, for example, any of triglycerin having a polymerization degree of n = 3, tetraglycerin having a polymerization degree of n = 4, and pentaglycerin having a polymerization degree of n = 5. However, the above “degree of polymerization” refers to “average degree of polymerization calculated from hydroxyl value” which has been widely used in the past.
Instead, the degree of polymerization of single polyglycerin itself was determined by gas chromatography, high performance liquid chromatography, or the like. The reason for limiting the degree of polymerization n to 3 to 5 is that the esterified product obtained using monoglycerin having a degree of polymerization of n = 1 or diglycerin having a degree of polymerization of n = 2 is inferior in hydrophilicity. This is because good quality products cannot be obtained. Conversely, an esterified product obtained by using a polyglycerin having a degree of polymerization n of 6 or more has good hydrophilicity but high foaming property, which causes inconvenience when used in an automatic dishwasher.

In order to obtain a polyglycerin containing 50% or more of a single polyglycerin having the above specific degree of polymerization,
Normally, for polyglycerin, which includes a non-reacted product having a variation in polymerization degree distribution, for example, molecular distillation, vacuum distillation using water vapor as a carrier, liquid chromatography, etc. are performed.
By removing or reducing a reactant having a lower molecular weight than the specific polymerization degree, the content ratio of the polyglycerin having the specific polymerization degree is increased.

The above-mentioned molecular distillation means that polyglycerol as a raw material is spread on a heat transfer surface in the form of a thin film with a centrifugal force, a brush or a roll, and the heat transfer surface is very small so that the evaporated molecules are hard to collide with each other. Under a high vacuum and high temperature conditions in a device having a condensing surface installed at a short distance, a low molecular weight substance is removed by utilizing the difference in vapor pressure of the substance.

The above-mentioned vacuum distillation is performed by performing distillation under high temperature and high vacuum using steam as a carrier and using a conventionally known vacuum apparatus such as a falling thin film vacuum distillation apparatus or a forced thin film vacuum distillation apparatus. This is to remove low molecular weight substances.

Further, the above-mentioned liquid chromatography means that a raw material, polyglycerin, is passed between two phases of solid particles and an effluent solvent packed in a column, and a low molecular weight substance is utilized by utilizing a difference in distribution coefficient. For example, a single column type or a simulated moving bed type can be used.

As the fatty acid to be reacted with the polyglycerin, the degree of polymerization n of a single polyglycerin contained in the polyglycerin by 50% or more is as follows.
The carbon number is within a certain range, that is, (2n) to (2n +
4) is used. Specifically, when the single polyglycerin is triglycerin (n = 3), a fatty acid having 6 to 10 carbon atoms is used, and tetraglycerin (n = 4) is used.
In the case of (1), a fatty acid having 8 to 12 carbon atoms is used, and in the case of pentaglycerin (n = 5), a fatty acid having 10 to 14 carbon atoms must be used. In particular, it is particularly preferable to combine fatty acids having 2n + 2 carbon atoms in relation to the degree of polymerization n of single polyglycerin.
As these fatty acids, as a saturated monocarboxylic acid,
Caproic acid (hexanoic acid: C = 6), caprylic acid (octanoic acid: C = 8), capric acid (decanoic acid: C = 1)
0), lauric acid (dodecanoic acid: C = 12), and myristic acid (tetradecanoic acid: C = 14).

As described above, the number of carbon atoms of a fatty acid is defined in relation to the degree of polymerization n of a single polyglycerin because the characteristics of the polyglycerol fatty acid ester are determined by the difference between the hydrophilic chain length and the hydrophobic chain length. In the present invention, when the fatty acid is a saturated fatty acid, the hydrophilic group chain length (H) / hydrophobic group chain length (L) is in the range of 1.3 to 2.4. Is preferable, and particularly, those having a range of 1.7 to 1.8 are preferable. In order to satisfy this range, it is necessary to define the relationship between the number of carbon atoms of the fatty acid and the degree of polymerization n of single polyglycerin as described above.

The above-mentioned hydrophilic group chain length (H) and hydrophobic group chain length (L) can be shown as follows, for example, by taking triglycerin caprylic acid monoester as an example.

[0023]

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The dry finishing agent for an automatic dishwasher of the present invention comprises an esterification reaction of the above-mentioned special polyglycerin with a specific fatty acid selected according to the degree of glycerin polymerization of a single polyglycerin contained therein. It contains a polyglycerin fatty acid ester obtained by the above-mentioned process, and is usually in a form of being dispersed and contained in water. In addition, from the viewpoint of storage stability and drying properties, those in which a part of water is replaced with a solvent such as ethanol are also included.

This product has a very good balance between low foamability and hydrophilicity required as a dry finish for automatic dishwashers, and has excellent wettability, dispersibility, solubilization, and the like. . Moreover, since it has excellent low-foaming properties and little foaming, it does not cause problems such as a decrease in water pressure when pumping liquid in an automatic dishwasher, and also does not deteriorate the finish of dishes due to foaming. .

Because of its excellent solubilizing properties, sorbitan fatty acid esters and the like which are conventionally relatively insoluble in water and are sometimes compounded with a solvent such as ethanol can be used without adding a solvent. Alternatively, an effective amount can be compounded by reducing the amount of the solvent. In addition, a bactericide or a deodorant such as polylysine, which could not be added in an amount sufficient to exert a sufficient effect because of its poor solubility, can be added in a larger amount than before, so that it has an excellent bactericidal action. Alternatively, a deodorizing function can be provided.

In the present invention, the content of the polyglycerin fatty acid ester in the dry finish is preferably set to 10 to 50% of the total amount. That is, if it exceeds 50%, the amount of the dry finishing agent remaining on the tableware after drying becomes large, and it is easy to cause traces like dirt itself. Conversely, if it is less than 10%, a sufficient finishing effect is obtained. It is difficult to obtain. In actual use, the amount of the polyglycerin fatty acid ester contained in the rinsing water is preferably from 7.5 to 150 mg / liter.

[0028]

As described above, the dry finish for an automatic dishwasher of the present invention contains a special polyglycerin fatty acid ester having a specific relationship between the degree of polymerization of polyglycerin and the carbon number of the fatty acid. Things. Therefore, the balance between low foamability and hydrophilicity required as a dry finish for automatic dishwashers is very good, and excellent wettability, dispersibility, solubilization, and the like are provided. Moreover, since it has excellent low-foaming properties and little foaming, there is no problem such as a decrease in water pressure when the liquid is fed by a pump in an automatic dishwasher. And, because it has excellent solubilizing properties, it is difficult to add a poorly soluble additive or a hardly soluble disinfectant or deodorant that was considered to be difficult to blend with a solvent. Since it can be blended to the extent that the effect can be sufficiently obtained without using or reducing the amount of the solvent, the added value of the dry finish can be increased while removing the solvent.

Next, examples will be described together with comparative examples.

[0030]

Examples 1 to 8 and Comparative Examples 1 to 3 Dry finishes having the compositions (weight basis, the same applies hereinafter) shown in Tables 1 to 3 below were prepared. Then, the low foaming property, the drying property and the transparency of the tableware of each dry finish were evaluated by the following methods. The results are shown in Tables 1 to 3 below.

[Low-foaming property] In a 200 ml measuring cylinder with a stopper, 50 ml of a sample adjusted to a concentration of 1% and 60 ° C. was placed, and
After being shaken upside down 0 times, it was allowed to stand, and the amount of generated bubbles was measured. And it evaluated based on the following criteria. ◎: 20 ml or less ○: more than 20 ml and 60 ml or less △: more than 60 ml and 100 ml or less ×: more than 100 ml

[Dryability] A plate-like glass test piece (50 mm × 100 mm × 2 mm thick) was added to 200 ml of the above-mentioned dry finish solution (concentration 0.005%, temperature 80 ° C.).
Was immersed for 30 seconds, then slowly pulled up and allowed to stand at room temperature, and the time required for water droplets and water films to disappear was measured. And it evaluated based on the following criteria. ◎: 1 minute or less ○: Over 1 minute and within 2 minutes △: Over 2 minutes and within 3 minutes ×: Over 3 minutes

[Clarity of tableware] Door type washing machine (JW
D-6, manufactured by IHI Co., Ltd.), ten tempered glass cups (HS tumbler, manufactured by Sasaki Glass Co., Ltd.) having a capacity of 170 ml were set at the center of the rack, and washed, rinsed and dried. Washing was performed using the standard concentration (0.12) of an automatic dishwasher detergent (Detershell Super, manufactured by T-Poll).
%) Solution was performed by spraying at 60 ° C. for 45 seconds. Rinse with the above dry finish (concentration 0.005)
%) Solution was performed by rinsing at 80 ° C. for 12 seconds. In addition, a pause of 3 seconds is provided between the washing and the rinsing. After rinsing, the glass was naturally dried at room temperature for 10 minutes, and then held over a fluorescent lamp to observe the surface condition. The evaluation criteria are as follows. ◎: No spots, excellent transparency and uniform finish. ：: Several drops, but transparency. △: Partial (more than half of the surface) spots, white and cloudy. ×: Surface. There are spots throughout and it is white and cloudy

[0034]

[Table 1]

[0035]

[Table 2]

[0036]

[Table 3]

From the above results, an esterified product of polyglycerin containing 60% of a single polyglycerin having a degree of polymerization of n = 3 to 5 and a fatty acid having a carbon number of (2n) to (2n + 4), especially (2n + 2), was used. It can be seen that the example products that were provided had excellent specifications. And it turns out that the esterification degree of a monoester and a diester is better than a triester.

[0038]

Examples 9 and 10, Comparative Examples 4 to 7 As shown in Tables 4 and 5, dry finishes were prepared using polyglycerol fatty acid esters having different contents of single polyglycerin. Then, the low-foaming property of each dry finish was evaluated in the same manner as described above. The results are shown in Tables 4 and 5 below. In addition, Example 5 described above is also shown for reference.

[0039]

[Table 4]

[0040]

[Table 5]

From the above results, the content of single polyglycerin contained in the polyglycerol fatty acid ester was 50%
If not, it will be understood that an excellent effect cannot be obtained as a dry finish.

[0042]

Examples 11 to 18 As shown in Tables 6 to 8 below,
Dry finishes with different loadings of polyglycerin fatty acid ester were prepared. Then, the low-foaming property of each dry finish was evaluated in the same manner as described above. The results are shown in Tables 6 to 8 below. In addition, the fifth embodiment described above.
Is also shown for reference.

[0043]

[Table 6]

[0044]

[Table 7]

[0045]

[Table 8]

From the above results, it was found that a single polyglycerin
It can be seen that the polyglycerin fatty acid ester containing 0% is preferably blended in an amount of 10 to 50%, especially 30% or more, based on the whole dry finish.

[0047]

Comparative Examples 8 to 10 As shown in Table 9 below, dry finishes were prepared using polyglycerin fatty acid esters having a low content of single polyglycerin. Then, the low-foaming property of each dry finish was evaluated in the same manner as described above.
The results are shown in Table 9 below. In addition, Example 5 described above is also shown for reference.

[0048]

[Table 9]

From the above results, it can be seen that the conventional dry finish using polyglycerin fatty acid ester having a wide distribution of polymerization degree has lower foaming property, drying property and transparency than the product of Example 5. Is inferior.

[0050]

Example 19, Comparative Examples 11 and 12 As shown in Table 10 below, a dry finish containing sorbitan caprylic acid monoester was prepared. Then, the low-foaming property of each dry finish was evaluated in the same manner as described above. The results are shown in Table 10 below.

[0051]

[Table 10]

From the above results, it can be seen that when the sorbitan fatty acid ester having poor compatibility with water is used in combination without adding ethanol, the product of Example 19 gives better performance.

[0053]

APPLICATION EXAMPLES 1-4 The dry finish of Example 5 was used, and the dilution ratio was changed as shown in Table 11 below. Then, the performance (low foaming property, etc.) when actually used as a dry finish in the rinse liquid was evaluated in the same manner as described above. The results are shown in Table 11 below.

[0054]

[Table 11]

From the above results, when the dry finish of the present invention is used as a rinsing liquid, it is preferable to dilute the polyglycerin fatty acid ester (surfactant) so as to have a concentration of 20 to 80 mg / liter. It can be seen that it is.

Continuation of the front page (56) References JP-A-60-53599 (JP, A) JP-A-4-244045 (JP, A) JP-A-7-100355 (JP, A) JP-A-8-143513 (JP) , A) JP-A-7-308560 (JP, A) JP-A-3-97791 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 1/00-17/08 B01D 12/00

Claims (2)

(57) [Claims] 1. A polyglycerin containing 50% by weight or more of a single polyglycerin having a specific polymerization degree n (n = 3, 4, or 5), and a carbon number of (2n) to (2n + 4)
A dry finish for an automatic dishwasher, comprising a polyglycerol fatty acid ester obtained by esterifying a fatty acid of the present invention. 2. The polyglycerin fatty acid ester according to claim 2,
The dry finish for an automatic dishwasher according to claim 1, wherein a fatty acid having (2n + 2) carbon atoms is used.